U.S. patent number 11,236,034 [Application Number 16/980,936] was granted by the patent office on 2022-02-01 for method for preparing acrylic acid.
This patent grant is currently assigned to Rohm and Haas Company. The grantee listed for this patent is Rohm and Haas Company. Invention is credited to Donald A. Ebert, Timothy Allen Hale, Brian Robert Keyes, Justin Rose, Jinsuo Xu.
United States Patent |
11,236,034 |
Ebert , et al. |
February 1, 2022 |
Method for preparing acrylic acid
Abstract
Provided is a process for preparing acrylic acid comprising (1)
preparing acrolein by catalytic gas phase oxidation comprising (a)
providing a reaction gas comprising (i) 5 to 10 mol % propylene,
(ii) 0.02 to 0.75 mol % propane, and (iii) 0.25 to 1.9 mol % of a
fuel mixture comprising at least one of methane and ethane, wherein
the molar ratio of the total amount of propane, methane, and ethane
to the total amount of propylene is from 0.01:1 to 0.25:1, (b)
contacting the reaction gas with a first mixed metal oxide catalyst
to form a mixture comprising acrolein, wherein the first mixed
metal oxide catalyst comprises one or more of molybdenum, bismuth,
cobalt, and iron, and (2) contacting the acrolein mixture with a
second mixed metal oxide catalyst to form a mixture comprising
acrylic acid, wherein the second mixed metal oxide catalyst
comprises one or more of molybdenum, vanadium, tungsten, copper,
and antimony.
Inventors: |
Ebert; Donald A. (Friendswood,
TX), Hale; Timothy Allen (Marshall, NC), Keyes; Brian
Robert (Houston, TX), Rose; Justin (Marvel, TX), Xu;
Jinsuo (Berwyn, PA) |
Applicant: |
Name |
City |
State |
Country |
Type |
Rohm and Haas Company |
Collegeville |
PA |
US |
|
|
Assignee: |
Rohm and Haas Company
(Collegeville, PA)
|
Family
ID: |
65911245 |
Appl.
No.: |
16/980,936 |
Filed: |
February 21, 2019 |
PCT
Filed: |
February 21, 2019 |
PCT No.: |
PCT/US2019/018876 |
371(c)(1),(2),(4) Date: |
September 15, 2020 |
PCT
Pub. No.: |
WO2019/182713 |
PCT
Pub. Date: |
September 26, 2019 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20200407306 A1 |
Dec 31, 2020 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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62645860 |
Mar 21, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C
51/252 (20130101); C07C 45/35 (20130101); C07C
51/252 (20130101); C07C 57/04 (20130101); C07C
45/35 (20130101); C07C 47/22 (20130101); C07C
57/04 (20130101) |
Current International
Class: |
C07C
51/25 (20060101); C07C 57/04 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0293224 |
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Nov 1988 |
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EP |
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1452227 |
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Sep 2004 |
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EP |
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1115052 |
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May 1968 |
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GB |
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2003064085 |
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Mar 2003 |
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JP |
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2014224068 |
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Dec 2014 |
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JP |
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2537302 |
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Dec 2014 |
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RU |
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Primary Examiner: Valenrod; Yevgeny
Assistant Examiner: Doletski; Blaine G
Attorney, Agent or Firm: Mutschler; Brian L.
Claims
What is claimed is:
1. A process for preparing acrylic acid comprising: (1) preparing
acrolein by catalytic gas phase oxidation comprising (a) providing
a reaction gas comprising (i) 5 to 10 mol % propylene, (ii) 0.02 to
0.75 mol % propane, and (iii) 0.25 to 1.9 mol % of a fuel mixture
comprising at least one of methane and ethane, wherein the molar
ratio of the total amount of propane, methane, and ethane to the
total amount of propylene is from 0.01:1 to 0.25:1; (b) contacting
the reaction gas with a first mixed metal oxide catalyst to form a
mixture comprising acrolein, wherein the first mixed metal oxide
catalyst comprises one or more of molybdenum, bismuth, cobalt, and
iron; and (2) contacting the acrolein mixture with a second mixed
metal oxide catalyst to form a mixture comprising acrylic acid,
wherein the second mixed metal oxide catalyst comprises one or more
of molybdenum, vanadium, tungsten, copper, and antimony.
2. The process of claim 1, wherein the fuel mixture comprises
methane.
3. The process of claim 1, wherein the reaction gas comprises
propylene in an amount of from 7.5 to 8.2 mol %.
4. The process of claim 1, wherein the reaction gas comprises
propane in an amount of from 0.03 to 0.62 mol %.
5. The process of claim 1, wherein the reaction gas comprises the
fuel mixture in an amount of from 0.5 to 1.4 mol %.
6. The process of claim 2, wherein the reaction gas comprises
methane in an amount of from 1.1 to 1.4 mol %.
7. The process of claim 1, wherein the molar ratio of the total
amount of propane, methane, and ethane to the total amount of
propylene is from 0.1:1 to 0.18:1.
8. The process of claim 1, wherein the first mixed metal oxide
catalyst comprises a primary component selected from the group
consisting of molybdenum, bismuth, and combinations thereof, and a
secondary component selected from the group consisting of cobalt,
iron, nickel, zinc, tungsten, phosphorous, manganese, potassium,
magnesium, silicon, aluminum, and combinations thereof, wherein the
primary component and secondary component are in an atomic ratio of
from 9:28 to 28:9, and wherein the second mixed metal oxide
catalyst comprises a primary component selected from the group
consisting of molybdenum, vanadium, and combinations thereof, and a
secondary component selected from the group consisting of tungsten,
cobalt, copper, and combinations thereof, wherein the primary
component and secondary component are in an atomic ratio of from
1:1 to 11:1.
9. The process of claim 1, wherein the fuel mixture comprises
sulfur in an amount of less than 30 parts per million by volume of
the fuel mixture.
10. A process for preparing acrylic acid comprising: (1) preparing
acrolein by catalytic gas phase oxidation comprising (a) providing
a reaction gas comprising (i) 7.5 to 8.2 mol % propylene, (ii) 0.03
to 0.62 mol % propane, and (iii) 0.5 to 1.4 mol % of a fuel mixture
comprising at least one of methane and ethane, wherein the fuel
mixture comprises sulfur in an amount of less than 30 parts per
million by volume of the fuel mixture, wherein the molar ratio of
the total amount of propane, methane, and ethane to the total
amount of propylene is from 0.1:1 to 0.18:1; and (b) contacting the
reaction gas with a first mixed metal oxide catalyst to form a
mixture comprising acrolein, wherein the first mixed metal oxide
catalyst comprises a primary component selected from the group
consisting of molybdenum, bismuth, and combinations thereof, and a
secondary component selected from the group consisting of cobalt,
iron, nickel, zinc, tungsten, phosphorous, manganese, potassium,
magnesium, silicon, aluminum, and combinations thereof, wherein the
primary component and secondary component are in an atomic ratio of
from 9:28 to 28:9; and (2) contacting the acrolein mixture with a
second mixed metal oxide catalyst to form a mixture comprising
acrylic acid, wherein the second mixed metal oxide catalyst
comprises a primary component selected from the group consisting of
molybdenum, vanadium, and combinations thereof, and a secondary
component selected from the group consisting of tungsten, cobalt,
copper, and combinations thereof, wherein the primary component and
secondary component are in an atomic ratio of from 1:1 to 11:1.
Description
FIELD OF THE INVENTION
This invention relates generally to a method for preparing acrylic
acid by catalytic gas phase oxidation. The method includes
providing a reaction gas containing propylene, propane, and a fuel
mixtures of at least one of methane and ethane, and contacting it
with a first oxidation catalyst to form a mixture containing
acrolein, and contacting the acrolein mixture with a second
oxidation catalyst to form a mixture containing acrylic acid.
BACKGROUND
Acrylic acid can be produced commercially by selective oxidation of
acrolein, which can be produced by selective oxidation of
propylene. Commercially available propylene can be divided into
different grades based on the levels of other impurities, e.g.,
refinery grade, chemical grade, and polymer grade. Depending on the
price differential, there can be an advantage to using one grade
over the other. While different grades of propylene can be used as
a feed in producing acrolein via catalytic oxidation, changing the
propylene grade from one to another can have a significant impact
on the fuel content of the absorber off gas, and can also be
prohibitive due to the fact that acrolein plants are typically
designed for a fixed propylene composition. For example, an
existing plant designed for Chemical Grade Propylene (containing 3
to 7% by volume propane as the main impurity) faces a few
challenges with high purity Polymer Grade Propylene (containing
less than 0.5% by volume propane as the main impurity): (1) a
shortage of propane fuel (an impurity in the propylene) that is
used as a fuel for downstream thermal oxidation of volatile
organics prior to venting into the atmosphere; and (2) a shortage
of propane as a ballast gas that moves the reactor feed composition
away from the flammable region.
Different propylene grades used as a feed gas for producing
acrolein have been utilized in the art. For example, WO 2014/195157
A1 discloses a method of producing acrolein with feed gas
containing Refinery Grade Propylene and a specified range of sulfur
and unsaturated hydrocarbons. The prior art does not, however,
disclose a method for preparing acrolein via gas phase oxidation by
providing a reaction gas according to the present invention which
allows for the use of a high grade of propylene in the reactor feed
gas for an existing plant designed for Chemical Grade Propylene
without sacrificing production rate or requiring other capital
improvements.
Accordingly, there is a need to develop a method that allows for
the use of a reactor feed gas containing a high grade of propylene,
while not suffering from the drawbacks of the shortage of fuel for
downstream thermal oxidation of volatile organics, and shortage of
a ballast gas that moves the reactor feed composition away from the
flammable region.
STATEMENT OF INVENTION
One aspect of the invention provides a process for preparing
acrylic acid comprising (1) preparing acrolein by catalytic gas
phase oxidation comprising (a) providing a reaction gas comprising
(i) 5 to 10 mol % propylene, (ii) 0.02 to 0.75 mol % propane, and
(iii) 0.25 to 1.9 mol % of a fuel mixture comprising at least one
of methane and ethane, wherein the molar ratio of the total amount
of propane, methane, and ethane to the total amount of propylene is
from 0.01:1 to 0.25:1, (b) contacting the reaction gas with a first
mixed metal oxide catalyst to form a mixture comprising acrolein,
wherein the first mixed metal oxide catalyst comprises one or more
of molybdenum, bismuth, cobalt, and iron, and (2) contacting the
acrolein mixture with a second mixed metal oxide catalyst to form a
mixture comprising acrylic acid, wherein the second mixed metal
oxide catalyst comprises one or more of molybdenum, vanadium,
tungsten, copper, and antimony.
Another aspect of the invention provides process for preparing
acrylic acid comprising (1) preparing acrolein by catalytic gas
phase oxidation comprising (a) providing a reaction gas comprising
(i) 7.5 to 8.2 mol % propylene, (ii) 0.03 to 0.62 mol % propane,
and (iii) 0.5 to 1.4 mol % of a fuel mixture comprising at least
one of methane and ethane, wherein the fuel mixture comprises
sulfur in an amount of less than 30 parts per million by volume of
the fuel mixture, wherein the molar ratio of the total amount of
propane, methane, and ethane to the total amount of propylene is
from 0.1:1 to 0.18:1, and (b) contacting the reaction gas with a
first mixed metal oxide catalyst to form a mixture comprising
acrolein, wherein the oxidation catalyst comprises a first mixed
metal oxide catalyst comprising a primary component selected from
the group consisting of molybdenum, bismuth, and combinations
thereof, and a secondary component selected from the group
consisting of cobalt, iron, nickel, zinc, tungsten, phosphorous,
manganese, potassium, magnesium, silicon, aluminum, and
combinations thereof, wherein the primary component and secondary
component are in an atomic ratio of from 9:28 to 28:9, and (2)
contacting the acrolein mixture with a second mixed metal oxide
catalyst to form a mixture comprising acrylic acid, wherein the
second mixed metal oxide catalyst comprises a primary component
selected from the group consisting of molybdenum, vanadium, and
combinations thereof, and a secondary component selected from the
group consisting of tungsten, cobalt, copper, and combinations
thereof, wherein the primary component and secondary component are
in an atomic ratio of from 1:1 to 11:1.
DETAILED DESCRIPTION
The inventors have now surprisingly found that acrylic acid can be
prepared from acrolein prepared by catalytic gas phase oxidation of
a reaction gas containing a high grade propylene while avoiding the
shortage of fuel for downstream thermal oxidation of volatile
organics, and the shortage of ballast gas that moves the reactor
feed composition away from the flammable region. Such drawbacks are
avoided by including a fuel mixture comprising at least one of
methane and ethane as a supplement to avoid the effects that would
otherwise result from using high grades of propylene containing
relatively lower amounts of propane as an impurity. Accordingly,
the present invention provides in one aspect a process for
preparing acrylic acid comprising (1) preparing acrolein by
catalytic gas phase oxidation comprising (a) providing a reaction
gas comprising (i) 5 to 10 mol % propylene, (ii) 0.02 to 0.75 mol %
propane, and (iii) 0.25 to 1.9 mol % of a fuel mixture comprising
at least one of methane and ethane, wherein the molar ratio of the
total amount of propane, methane, and ethane to the total amount of
propylene is from 0.01:1 to 0.25:1, (b) contacting the reaction gas
with a first mixed metal oxide catalyst to form a mixture
comprising acrolein, wherein the first mixed metal oxide catalyst
comprises one or more of molybdenum, bismuth, cobalt, and iron, and
(2) contacting the acrolein mixture with a second mixed metal oxide
catalyst, wherein the second mixed metal oxide catalyst comprises
one or more of molybdenum, vanadium, tungsten, copper, and
antimony.
The inventive process comprises providing a reaction gas that is
contacted with an oxidation catalyst to form a mixture containing
acrolein. The reaction gas contains propylene, propane, and a fuel
mixture containing at least one of methane and ethane. The reaction
gas contains propylene in an amount of from 5 to 10 mol %,
preferably from 6.5 to 9 mol %, and more preferably from 7.5 to 8.2
mol %, based on the total volume of the reaction gas. The reaction
gas contains propane in an amount of from 0.02 to 0.75 mol %,
preferably from 0.02 to 0.65 mol %, and more preferably from 0.03
to 0.62 mol %, based on the total volume of the reaction gas. The
reaction gas contains a fuel mixture containing at least one of
methane and ethane in an amount of from 0.25 to 1.9 mol %,
preferably from 0.4 to 1.6 mol %, and more preferably of from 0.5
to 1.4, based on the total volume of the reaction gas. In certain
embodiments, the reaction gas contains methane in an amount of from
0.5 to 1.9 mol %, preferably from 0.8 to 1.6 mol %, and more
preferably of from 1.1 to 1.4 mol %, based on the total volume of
the reaction gas. In certain embodiments, the molar ratio of the
total amount of propane, methane, and ethane in the reaction gas to
the total amount of propylene in the reaction gas is from 0.1:1 to
0.25:1, preferably from 0.1:1 to 0.2:1, and more preferably from
0.1:1 to 0.18:1.
The reaction gas further contains an oxidant for the oxidation of
propylene to acrolein, and acrolein to acrylic acid. Suitable
oxidants include, for example, oxygen (O.sub.2). Suitable sources
of oxygen include, for example, air or a source that contains a
higher purity of O.sub.2. In certain embodiments, the molar ratio
of O.sub.2 to propylene is in the range of from 1.6:2.2, preferably
from 1.7:2.0.
The reaction gas of the inventive process is contacted with an
oxidation catalyst--a first mixed metal oxide catalyst. Mixed metal
oxides catalysts that are known in the art, e.g., as described in
U.S. Pat. Nos. 6,028,220, 8,242,376, and 9,205,414. Suitable first
mixed metal oxide catalysts include, for example, those including
one more of molybdenum, bismuth, cobalt, iron, nickel, zinc,
tungsten, phosphorous, manganese, potassium, magnesium, silicon,
and aluminum. In certain embodiments, the first mixed metal oxide
catalyst comprises one or more of molybdenum, bismuth, cobalt, and
iron. In certain embodiments, the first mixed metal oxide catalyst
comprises primary and secondary components in an atomic ratio of
from 9:28 to 28:9, preferably from 11:28 to 20:9, and more
preferably of from 13:28 to 14:9. In certain embodiments, the
primary component comprises one or more of molybdenum and bismuth.
In certain embodiments, the secondary component comprises one or
more of cobalt, iron, nickel, zinc, tungsten, phosphorous,
manganese, potassium, magnesium, silicon, and aluminum.
In certain embodiments, the fuel mixture contains methane that is
sourced from natural gas that includes impurities that are
detrimental to the oxidation catalyst, e.g., catalyst poisons such
as various sulfur compound (e.g., H.sub.2S, dimethyl sulfide,
carbonyl sulfide, mercaptans, and the like). Gas containing such
catalyst poisons are known in the art as "sour gas." Sour gas can
be "sweetened" by removing such sulfur compounds from the natural
gas. Sulfur compounds can be removed it their presence has negative
impacts on the catalyst performance, or downstream thermal
oxidizer. Suitable sulfur removal technologies are known in the art
and include, for example, by flowing the natural gas through a
fixed bed packed with absorbent materials. In certain embodiments,
the fuel mixture contains sulfur in an amount of less than 30 parts
per million by volume of the fuel mixture, preferably less than 5
parts per million, more preferably less than 1 part per million,
and even more preferably less than 0.1 part per million, by volume
of the fuel mixture.
In certain embodiments, the inventive process step of contacting
the reaction gas to form a mixture comprising acrolein comprises
passing the reaction gas through a reactor tube or through a
plurality of reactor tubes in parallel, each of which is filled
with the first mixed metal oxide catalyst. In certain embodiments,
the one or more reactor tubes are charged with the first mixed
metal oxide catalyst to a length of from 1 to 7 meters, preferably
from 2 to 6 meters, and more preferably of from 3 to 5 meters. In
certain embodiments, the internal diameter of each reactor tube is
in the range of from 15 to 50 mm, preferably 20 to 45 mm, and more
preferably of from 22 to 40 mm.
The preparation of acrylic acid further comprises contacting the
acrolein mixture obtained by the inventive process described above
with a mixture of oxidation catalysts--the first mixed metal oxide
catalyst described above and a second mixed metal oxide catalyst to
produce a mixture containing acrylic acid. Suitable second mixed
metal oxide catalysts are known in the art, e.g., as described in
U.S. Pat. Nos. 4,892,856 and 6,762,148, and include, for example,
one or more of molybdenum, vanadium, tungsten, copper, and
antimony. In certain embodiments, the second mixed metal oxide
catalyst comprises primary and secondary components in an atomic
ratio of from 1:1 to 11:1, preferably from 2:1 to 9:1, and more
preferably of from 3:1 to 7:1. In certain embodiments, the primary
component comprises one or more of molybdenum and vanadium. In
certain embodiments, the secondary component comprises one or more
of tungsten, copper, and antimony.
In certain embodiments, the inventive process step of contacting
the reaction gas to form a mixture comprising acrolein comprises
passing the reaction gas through a reactor tube or through a
plurality of reactor tubes in parallel, each of which is filled
with a mixture of the first mixed metal oxide catalyst and the
second mixed metal oxide catalyst. In certain embodiments, the one
or more reactor tubes are charged with mixed metal oxide catalysts
to a length of from 1 to 7 meters, preferably from 2 to 6 meters,
and more preferably of from 3 to 5 meters. In certain embodiments,
the internal diameter of each reactor tube is in the range of from
15 to 50 mm, preferably 20 to 45 mm, and more preferably of from 22
to 40 mm.
Some embodiments of the invention will now be described in detail
in the following Examples.
EXAMPLES
Example 1
Characterization of Thermal Oxidation Constraints on Exemplary and
Comparative Processes
A conventional two stage single pass acrylic acid process is
operated with typical conditions on Chemical Grade Propylene
("CGP"), Polymer Grade Propylene ("PGP"), and PGP with supplemental
fuel, as recited in Table 1.
TABLE-US-00001 TABLE 1 Thermal Oxidation Constraints on Exemplary
and Comparative Processes Operation Operation Operation w/PGP +
fuel w/CGP w/PGP injection Relative C.sub.3H.sub.6 Rate 100 72 100
(% of maximum) C.sub.3H.sub.6 Purity (mol %) 94.50 99.50 99.50
C.sub.3H.sub.6 Concentration 8.0 8.0 8.0 (mol %) C.sub.3H.sub.8
Concentration 0.47 0.04 0.05 (mol %) Supplemental C.sub.1-C.sub.3
0.00 0.00 1.07 Fuel Concentration (mol %) Total C.sub.1-C.sub.3
Fuel 0.47 0.04 1.11 Concentration (mol %) C.sub.3H.sub.6 Conversion
96.0 96.0 96.0 (%) Residual Acrolein 0.50 0.50 0.50 Yield (%) Total
C.sub.1-C.sub.3 0.058 0.005 0.139 fuel:propylene (mol ratio)
AOG.sup.+ Heating 33 18 33 Value (Btu/SCF) Thermal Oxidizer 965 964
965 Firebox Temperature (.degree. C.) Stack O.sub.2 (mol %) 2.95
2.94 2.94 Tox Burner Capacity 100 100 100 (%) .sup.+"AOG"
represents the Absorber Off Gas
The results demonstrate that the process is constrained by energy
input to the thermal oxidizer. Operation with the above conditions
results in a vapor waste stream containing 30 to 40% of the energy
input to the thermal oxidizer. As the purity of the propylene
feedstock increases, the energy content in the vapor waste stream
decreases. At the extreme case of a polymer grade propylene feed
with propylene 99.5% minimum, the energy content in the vapor waste
stream is 50% of what it was with CGP. Without any other process
changes, the plant production capacity would have to be decreased
by 20-30% to maintain the desired thermal treatment conditions.
To avoid the rate reduction from the energy input limitation,
natural gas (or C.sub.1 to C.sub.3 fuel) is injected into the
process at a 0.14:1 molar ratio with propylene. The energy no
longer provided by the "impurities" in the propylene is replaced
with energy from lower cost methane. This allows the plant to
operate with a high purity feedstock while maintaining the
operating rate, realizing a reduction in energy cost to operate the
thermal treatment unit, and avoiding capital modification of
thermal treatment unit.
Example 2
Characterization of Flammability Constraints on Exemplary and
Comparative Processes
One hazard inherent in the oxidation of propylene is the management
of hazards associated with the flammability of propylene. This
hazard can be managed by operating with a reactor feed composition
outside of the flammable region by some margin of safety. The
distance between the operating point and the flammable region is
defined as the approach to the flammable limit. Margins of safety
exist to cover error in flammable boundary correlations, errors in
determination of reactor feed composition, and to prevent reactor
trips associated with disturbances in reactor feed flows. The
reactor feeds are manipulated such that the feed composition is
moved above the upper flammable limit without passing through the
flammable region. When one is above the flammable limit, increasing
fuel content tends to increase the oxygen required to create a
flammable mixture (more fuel increases the distance to the
flammable limit). In a propylene partial oxidation process,
propylene concentration cannot be increased independently because
oxygen is required in a particular molar ratio (typically greater
than 1.4:1) to propylene to complete the desired chemical reaction.
Because of the oxygen to propylene constraint, the oxygen
concentration must also increase when C.sub.3 concentration
increases. The net result of increasing propylene concentration at
constant oxygen to propylene ratio is moving closer to the
flammable region. A conventional two stage acrylic acid process
with Absorber Off Gas recycle is operated with typical conditions,
as recited in Table 2.
TABLE-US-00002 TABLE 2 Flammability Constraints on Exemplary and
Comparative Processes Operation Operation Operation w/PGP + fuel
w/CGP w/PGP injection Relative C.sub.3H.sub.6 Rate 100 94.5 100 (%
of maximum) C.sub.3H.sub.6 Purity (mol %) 94.50 99.50 99.50
C.sub.3H.sub.6 Concentration 7.7 7.4 7.7 (mol %) C.sub.3H.sub.8
Concentration 0.58 0.05 0.05 (mol %) Supplemental C.sub.1-C.sub.3
0.00 0.00 1.28 Fuel Concentration (mol %) Total C.sub.1-C.sub.3
Fuel 0.58 0.05 1.33 Concentration (mol %) C.sub.3H.sub.6 Conversion
96.5 96.5 96.5 (%) Residual Acrolein 1.00 1.00 1.00 Yield (%) Total
C.sub.1-C.sub.3 0.075 0.007 0.173 fuel:propylene (mol ratio) AOG
Heating 28 15 28 Value (Btu/SCF) Thermal Oxidizer 899 899 898
Firebox Temperature (.degree. C.) Stack O.sub.2 (mol %) 2.1 2.1 2.1
Tox Burner Capacity 70 100 70 (%) Approach to minimum minimum
>minimum Flammable Limit Compressor 100 100 100 Capacity (%)
The results demonstrate that the process is simultaneously
constrained by the ability of the compressor to pump mixed gas
(air+recycle) to the reactor, the propylene concentration in the
reactor feed, and the oxygen in the reactor outlet. Each one of
these constraints represents a significant boundary. In turn, it is
not possible to increase the capacity of a compressor without
making capital investment. Operating too closely to the flammable
region risks a process disturbance that could cause fire with
significant safety and economic impact. If adequate excess oxygen
is not maintained in the reactor outlet, it may cause the catalyst
to age prematurely or cause incomplete conversion of acrolein to
acrylic acid and high levels of acrolein fed to the thermal
oxidizer. Insufficient oxygen could potentially cause a release of
acrolein if the thermal oxidizer is unable to handle the increased
acrolein loading. Thus, in a process constrained as defined above
and operated at the conditions defined above, the maximum operating
rate has to be reduced by 5% (on propylene basis) when the
propylene purity increases. By injecting natural gas into the
propylene at 0.17:1 C1 to C.sub.3:C.sub.3H.sub.6 molar ratio, the
maximum rate can be maintained with higher purity of propylene. In
addition, the "approach to flammability limit" is moved further
away from the flammable region. The advantage of having an inert
fuel present in the reactor is regained.
* * * * *